Condensation products and process of producing same



Patented Mar. 22, 1938 GONDENSATION PRODUCTS AND PROCESS 0F PRODUCINGSAME Herbert Hiinel, viennmhustrla, assi nor to Beimuth Bcichhold,Detroit, Mich., doing business as Reichhold Chemicals No Drawing.Original application December 20, 1934, Serial No. 758,502, now Patent2,079,210.

Divided and this application October 8, 1935 Serial No. 44,126

6 Claims.

The invention relates to condensation products of thephenol-aldehydetype, and to combinations of such products with substantially neutralresins, fatty oils, waxes and otherester-like bodies.

The claims of'the present application are directed to the preparation ofvarnish making substances having a particularly high alkali resistance,which substances are obtained by reacting at least one material selectedfrom the group consisting of substantially neutral varnish raw materialsand waxes, (referred to in my Patent No. 2,058,797 dated October 27,1936) with a heat hardening condensation product of the phenolformaldehyde type formed by condensing by the cations Serial No.218,587, filed September 9,

aid of a strongly alkaline catalyst, asubstantial excess of formaldehydeover the equimolecular' quantity, and a special phenol having aplurality of substituents, the characteristicsmf which will be morefully set forth.

"The present application is a division of my application Serial No.758,502 filed December 20,

1934, now Patent No. 2,079,210, which is a continuation in part ofmy'applications Serial Nos. 609,337, flied May 4, 1932, for Condensationproducts and process for preparing same, now Patent No. 2,049,447, datedAug. 4, 1936 and 643,794, filed November 21, 1932, for Process for theproduction of oil-soluble phenol aldehyde resins which now PatenhNo.2,012,277, dated August 27, 1935,

which in turn are divisions of my earlier appli- 1927, now.Patent No.1,800,295, dated April 14, 1931, and Serial No. 362,460, filed May 11,1929, now Patent No. 1,800,296, dated April 14, 1931. It has been shownin these applications that homogeneous products may be obtained frominteraction of certain hardening phenol formaldehyde condensationproducts and substantially neutral resins, fatty oils, waxes and otheresterlike bodies. The interaction products prove to be of particularvalue in the varnish and lacquer field and for similar purposes. Thephenol condensation products, whether they are crystalline, liquid,viscous or already in a solid resinous form, due to their relatively lowmolecular weight, are

readily soluble in common solvents. They are obtained from a substantialexcess of formaldehyde over the equimolecular proportion, and phe- (cl.zoo-4i nols having only two of the reaction favorable positions in themolecule unoccupied, with the aid of a strong alkaline catalyst whichis-neutralized after the chemical combination has taken place. Thephenols may be monovalent or polyvalent, mononuclear or polynuclear, thereaction favorable positions being the orthoand" parapositions to thephenolic hydroxy group or groups, respectively. a

It has further been shown that such condensation products as derive fromphenols carrying at least one higher aliphatic or hydroaromatic, or

generally speaking, one higher saturated hydro carbon radical, are wellcompatiblewith drying oils. These phenols may also be applied in mixturewith other phenols not carrying such a radical, the total number of theunoccupied reaction favorable positions also being two.

Now I have found that as a rule the number of such saturated carbonatoms of the substituting group or groups, respectively, preferablyshould not be lower than three per each phenolic hydroxyl group of thephenolused, in order to secure sufficient oil compatibility of thehardening condensation product. In this case even the maximumproportion, that is to say two mols of formaldehyde per one mol. of thephenol, may be chemically combined, yielding a condensation product ofparticularlyhigh hardening eiiect when reacted with neutral resins,fatty oils, etc., as described in my specifications above mentioned.

This, however, does not mean that phenols carrying a lower alkyl areentirely inoperative for my process. So for instance, para-ethylphenol,when condensed with an excess of formaldehyde, yields a hardeningcondensation product which is fairly compatible with China-wood oil, butonly when condensed without excess or with a relatively small excess offormaldehyde is the condensation product obtained easily compatible withother dryfiig oils. The condensation product, however, in this case doesnot show the maximum of hardening capacity which otherwise isattainable.

The general rule regarding thenumber of allphatic' carbon atoms whichshould be present to secure good solubility in oils also applies tophenols carrying mixedaliphatic-aromatic hydrocarbon radicals, such asaralkyls. For illustration I mention that para-cumyl phenol (4- hydroxydiphenyl-dimethyl-methane), behaves similar -to para-isopropyl-phenol,in that it yields, even when condensed with a maximum proport on offormaldehyde. arde B ows which are fairly compatible with drying oils ofany kind, including bodied oils. The para-benzylphenolfiyields only.hardening condensation products of limited compatibility with dryingoils, and behaves in a manner similar to para-ethylphenol. Frompara-phenyl-phenol (i-hydroxy diphenyD' only oil compatible condensationproducts may be formed which have no hardening character or only to aslight degree. This phenol behaves in a similar manner to para-cresoland is slightly superior as regards the oil compatibility of thecondensation products obtained therefrom.

In all these cases, the corresponding ortho compounds behave similarlyto the para compounds, but it should be pointed out that condensationproducts from ortho-cresol show far poorer oil solubility than thosefrom para-cresol. provided conditions are equal.

Further investigations have proved that methyl groups in meta positionswhich are present in addition to hydrocarbon groups in one of thereaction favorable positions, in certain cases do not increase thecompatibility of the hardening condensation products with drying oils.80 1,2, xylenol is not superior to para-cresol. Benzylmeta-cresols,which are obtained from metacresol and benzyl-chloride, yield ahardening condensation product which shows even less oil compatibilitythan a corresponding one from paraor ortho-benzyl phenol. Also thebenzyl compounds which are obtained from 1,3,5 symmetric xylenol andbenzyl-chloride do not yield condensation products of superior oilcompatibility when condensed with an excess of formaldehyde, as comparedwith corresponding condensation products from benzyl phenols. Thesebehaviours are probably due to the fact that methyl groups inmeta-position influence the activity of the hydrogen atoms in thereaction favorable positions of phenols. A superior activity is alsoshown up by meta-cresol in comparison to phenol itself; the meta-cresoltherefore condenses with aldehydes, as is known, considerably fasterthan phenol. This, however, does not apply to the presence of higherhydrocarbon groups in metapositions, since, as has been shown by myPrior patents, good results are obtained also from phenols carrying ahigher hydrocarbon radical in a non-reaction favorable position, that isto say, in a meta-position to the phenolic hydroxy groups, as long asthe general rule holds true that only two reaction favorable positionsare unoccupied. So for instance, condensation products from carvacrolwhich carries the isopropyl group in meta-position and the methyl groupin orthoposltion show equal compatibility with oils as condensationproducts from corresponding amounts of formaldehyde and theisomericthymol which carries the isopropyl group win one of the reactionfavorable ortho-positions while the methyl-group is in one of themetapositions.

Another example of phenol which carries the substituent, securing oilcompatibility in one of the meta-positions, and which yieldscondensation products well adaptable for my process, ispara-chloro-m-tertiary-butyl-phenol. Also two ethyl groups in themeta-positions may secure oil compatibility of the hardeningcondensation product-or even one ethyl group in a meta-position inaddition to a methyl group in one of the reaction favorable positions.Good results are obtained, e. g. from 3,4 diethyl phenol, 3,5 diethyl 4chloro-phenol or 4 methyl 3 ethyl phenol.

Hardening condensation products which a e derived from phenols carryingsubstituents in meta-position behave to exceptional advantage, inasmuchas they finally lead to condensates of particularly hi h alkaliresistance. This is also shown by the interaction products which areobtained from these condensation products with drying oils. t

I have found further that, as a rule, also in the case ,of polyvalentphenols, three aliphatic or hydroaromatic carbon atoms should be presentfor each phenolic hydroxy group to secure good compatibility with oils.According to the general rule, however, only two of the reactionfavorable positions must be unoccupied at the same time. By the presenceof a second phenolic hydroxy group in the benzene ring, the chemicalbehaviour is appreciably changed and not entirely comparable with thosein the mono-hydroxy-benzone. It is, however, easily understood that inthe catechol the two orthoand two para-positions to the phenolic groupsare to be considered as reaction favorable positions. The same appliesto the hydro-quinone, which has four orthopositions to the hydroxygroups. The formulae .below indicate the reaction favorable iositions:

on on on o 0 P on It can be seen from this that 'two of these reactionfavorable positions must be occupied by substituents in order to complywith the general rule. For instance, tertiary-butyl groups are easilyintroduced according to known methods. The resulting products usuallyare viscous bodies with very little tendency to crystallize because acomplicated mixture of isomers is present.

The di-butyl-catechol and di-butyl-hydroon \AY It seems that thesepositions may be considered as reaction favorable positions of doubleactivity. It is, for instance, a matter of fact that resorcin reactsunusually fast with formaldehyde. On the other hand, the position shouldnot be a reaction favorable one, since it is in meta-position to bothphenolic hydroxy groups. Now it has also been found that resorcin mustcarry two substituents in order to comply with the general condition.Then it, behaves like its double substituted isomers, mentioned above,or like suitably substituted monovalent phenols. In other words, in theresorcin the meta-position 5 functions as a reaction favorable position.Suitable derivatives 55 ployed which, when condensed by themselves, do

1 tive in my process, such as suitable derivatives of thedihydroxy-diphenyl-methane.. Two of its four reaction favorableortho-positions to the phenolic groups must be occupied, .Inorder tosecure suflicient oil-solubility of hardening condensationproductsprepared from such phenols and an excessof formaldehyde over theequimolecular quantity, the average number of saturated carbon atomsfigured for each phenolic group should be 3 or more, according to therule stated aboved The number of aliphatic or hydroaromatic carbon atomsrequired may be represented by groups substituted in the ortho-positionsor also by groups replacing thev hydrogen. atoms of the methylene group.Suitable derivatives of this type are obtained in a known manner fromthe cheap ortho-cresol and a higher carbonyl compound, such asbutyl-aldehyde or methyL-ethylketone, or still higher homologues withthe aid of an acid catalyst. The phenolic'bodies obtained lead tohardening condensation products when .operating in the described way,which show good or at least fair compatibility with oil. The ketonesmentioned before are now easily available in comparatively. cheapmaterials.

It has been shown by my prior applications that suitable polynuclearphenols are also obtained from orth-c-cresol. andhydro-aromatic-carbonyl compounds, such as cyclo-hexanone or thetechnical mixture of the methyl-cyclo-hexanones. These phenols contain aclosed chain radical.

The ortho-cresol may be replaced wholly or in partby the para-cresol,which, however, is not as cheap as ortho-cresol.

The orthoand p'ara-cresol may also be replaced by their homoiogues, suchas the corresponding ethyl phenol. The number of carbon atoms of thealiphatic carbonyl compounds may be reduced in these cases, or evenaromatic carbonyl compounds may be used. In all these cases described inthe foregoing paragraphs, the reresulting crude reaction products suitmy process.

Crystalline bodies are seldom obtained, especially since the ketonesemployed are technical mixtures of isomers.

I havepreviously, pointed out in my aforesaid specifications that, inaddition to such phenols, which due to the high molecular saturatedsubstituents, yield a readily oil soluble hardening condensationproduct, phenols may also be emnot yield hardening condensation productsof sufiicient compatibility with drying oils. The phenols, however, mustcomply with the general rule, that is tosay,they must have only tworeaction favorable positions left unoccupied. Now I have also found tobe a rule in this case, that when a mixture of phenols is condensed, thetotal number of saturated carbonatoms divided by the number of thephenolic groups should preferably be 3 or more, in order to securesufllcient ,oompatibility of the hardening condensation products withdrying oils. So for instance, equimolecular proportions of para-ethyland para-butyl phenol, and para-cresol and para-amyl phenol yieldcondensation products which are sufficiently compatible with any dryingoil even when possessing the maximum hardening effect. The same applies,for instance, toan equimolecular mixture of para-cyclohexyl phenol andpara-chioro phenol.

A non-phenolic benzene ring as substituent may be counted as equivalentof 1 to 2 aliphatic saturated carbon atoms. So for instance, the mixtureof 2 mols para-phenyl phenol and 1 mol.

para-hexyl phenol leads to about equal results as the mixture mentionedabove. Other examples of mixtures of 2 or more phenols are:

mols p-amyl-phenol and 1 mol. p-benzyl-phenol or V 1 mol. p-hexyl-phenoland 3 mols p-benzyl-phenol 1 mol. 1 mol.

dibutyl catechol and 1,2,4 xylenol mol. mol. mol.

octyl-phenol and p-cresol and p-chloro-m-cresol In the foregoingexamples the para compounds may be replaced by the corresponding orthocompounds. Instead of condensing the mixture .of

phenols with formaldehyde,separately prepared" formaldehyde condensationproducts of the single phenols may be mixed or heated together aftermixing if higher stages of condensation are desired, as described in myearlier specifications. As set forth in my older specificationsmentioned hereinbefore and in my Patents Nos. 1,800,295 and 1,800,296,the condensation of the phenols or mixtures of them is efiectedaccording to the method of Lederer and Manasse, preferably by leavingthe phenols, aqueous formaldehyde and a strong alkaline catalyst incontact for a prolonged period of time. The process includes the carefulneutralization or slight acidification of the reaction mixture, whichaction should only be done after the phenol and the formaldehyde arecombined. These .tWo components should form a uniform solution with theaid of a catalyst. In some cases inert solvents, such as alcohols ormixtures of alcohol and benzene, etc., should be added to secure a.uniform solution and continual contact of the reacting components. Theaqueous formaldehyde in these cases should be replaced by its anhydrousforms wholly or in' part. Such a procedure preferably applies to phenolswhich; on account of substituents in meta-positions, tend tocondensation products having low solubility in caustic solutions.

It has been proved that as a rule all phenols having two reactionfavorable positions in the molecule are capable of combining up to suchamounts of formaldehyde which correspond to 2 mols. In this case, thecondensation product obtained shows maximum hardening effect, as saidbefore. When carrying out the condensation at low temperatures frommaximal proportionsof formaldehyde the corresponding phenol dialcohol isobtained. However, in order to accelerate this reaction still largeramounts of formaldehyde may be used, but finally not more than 2- molsof form- Canizzaro reaction. The uncombined formaldehyde may be regainedin a suitable way.

The final condensation productsare crystalline, liquid, or are more orless viscous when ordinary or slightly elevated temperatures have beenapplied dui'ing the condensation. They are of solid resinous form whenelevated temperatures have been applied for a prolonged time. Thepreferred way to form such solid resinous products, however, consists informing first an especially lowmolecular liquid condensation product andin subjecting this product after neutralization to a temperaturepreferably higher than 100 C.

A few examples may illustrate my process. However, my process is not tobe restricted to these examples, as they are only to be considered asillustrations. The aqueous formaldehyde referred to is .the commercial40% solution by volume. The temperatures are in degrees centigrade.

Example 1 61 gm. para-ethybphenoi and 53 gm. of aqueous formaldehyde arecondensed by leaving them in contact in the presence of caustic liquidcorresponding to about 5 gm. NaOH. After a few days the two componentsare combined and after neutralization form a low viscous condensationproduct.

' When this product is heated with approximately twice as muchChina-wood oil to temperatures of about 150 C. or higher a uniform massis gradually formed with the evolution of steam. If the reaction mixtureis cooled, while still reacting, shortly after it shows homogeneity inthe hot state, most of the phenolic condensation product precipitatesout from its solution, but after the reaction has been completed, whichsuitably should be done between 200-230 C., a permanently homogeneousclear interaction product is obtained. Its external appearance is thatof a highly viscous oil which is soluble in all ordinary varnishsolvents, including petroleum distillates in which the phenoliccondensation product itself is entirely insoluble.

The condensation product as obtained above may also be heated alonefirst to temperatures of about 150 C. until a solid resinouscondensation product is obtained. This forms homogeneous eactionproducts with China-wood oil in a way quite similar to the still liquidcondensation product. When heating the condensation product (onepart)with rosin-glycerine-ester (four parts) to about 240 C., a homogeneousproduct is obtained, the melting point of which is about 25- 30 C.higher than that of the rosin-ester. This means that the condensationproduct does not possess the highest obtainable hardening effect. Boththe liquid and the solid condensation product, when heated with linseedoil or the like, only enter into solution at about 180-190 C. At thistemperature, however, the condensation product is converted into theinfusible stage so that in some cases only an incomplete combination ofthe condensation product with linseed oil takes place. In order toobtain condensation products which are compatible with bodied linseedoil, the rate of chemically combined formaldehyde must be reduced stillmore.

Example 2 parts of a mixture of 'orthoand paraisopropylphenol, parts ofaqueous formaldehyde, 12 parts of caustic soda solution (40%) are leftin contact at room temperature until chemical combination has takenplace, which requires about two weeks. The amount of formaldehydecorresponds to 2 mols per 1 mol. of the pheml. After neutralization, aliquid condensation product is obtained which may be converted byfurther condensation'under action of heat into a solid resinouscondensation product. Both the dried liquid and the solid productdissolve in a multiple quantity of China-wood oil at about 100 0.,forming a solution that separates on cooling. When heated above. C.considerable reaction sets in, and when heating is continued for asufficient time, a uniform, permanently clearrcaction product isobtained. If the reaction is carried to completion such as is suitablydone within about hour at temperatures of about 220' C.. a highlyviscous product is obtained. The increase of viscosity, due to thecondensation reaction, is so great that at least two parts of Chinawoodoil to one part of the condensation product should be used to-avoidgelatinization.

The phenolic condensation, product also dissolves in linseed oil andsimilar oils at temperatures of about 150 0.,and separates out oncooling. By prolonged heating above 150 C.. or in for shorter time above200 C., a permanently clear interaction product is obtained.

In bodied oils the condensation products dissolve only at about C. atthe same time combining with the oil and forming homogeneous reactionproducts. The increase of viscosity. due to the reaction, is so enormousthat 6 to 10 parts or even more, of the bodied oil have to be taken toavoid gelatinization, the minimum proportion depending on the originalviscosity of the oil.

By heating the condensation product (one part) with four parts ofrosin-ester in the way described above, a resin is obtained, the meltingpoint of which is about 55-60 C. higher than that of the rosin-ester.

Example 3 Very similar condensation products are obtained by condensinga mixture of 4 parts paraethyl-phenol and 5 partspara-tertiary-butylphenol with 11 parts of aqueous formaldehyde or more,or by condensing a mixture of 2 parts para-cresol and 3 partspara-tertiary-amyl-phenol with 6 parts formaldehyde or more in a waysuch as described in the foregoing examples. The proportions givencorrespond to about equimolecular quantities of the phenols in themixture used and to a double molecular quantity of formaldehyderespectively, and might be varied ,slightly. The solubility conditionsand hardening effect of the condensation products are very much likethose of the condensation products obtained in Example 2, the varnishesshowing excellent color retention, which is due to the exclusive use ofpara-substituted-phenols.

Instead of forming condensation products from mixtures of phenols, alsothe corresponding condensation products separately formed, for instancedialcohols, may be mixed after having been neutralized. The mixture ofdialcohols, etd. may be heated above 100 C. if a solid condensationproduct is desired.

' Example 4 50 parts chemically pure para-benzyl-phenol of a meltingpoint of 84, 30 parts commercial formaldehyde solution, 4 parts of NaOH,or equivalent amounts of KOH, etc., are left in contact for about 3days, after which time chemical combination has taken place. Byneutralization or slight acidification, a liquid condensation 2,112,022product is obtained which may be converted into further condensaing tothe methods described, show properties very similar tothat' of thecondensation products obtained according to Example 1. It is.

however, also possible to react them with linseed oil or similar dryingoils at temperatures above 160. C., whereby homogeneous reactionproducts are obtained. The condensation products do not show the maximumhardening effect due to the relatively small excess of formaldehyde.

Example 5 Equal parts by weight of para-cumyl-phenol (4hydroxy-diphenyl-dimethyl-methane) and aqueous formaldehyde, andsufilcient amounts of caustic alkali to form a clear solution, aretreated in a manner corresponding to any of the preceding examples. Theformaldehyde employed corresponds to a considerable excess over 2 molsper 1 mol. of the phenol, said 2 mols being the maximum quantity thephenol used is capable of combining. After about one week's standing atroom temperature, or slightly'elevated temperature, this maximumquantity has chemically combined. The condensation product finallyobtained, which is liquid or solid, depending on the temperature used,shows very slmilar properties and behaviour with regard to solubility inthe difierent types of drying oils and the high degree of hardeningeffect as the condensation products obtained in Examples 2 or 3.

Example 6 55 gm; catechol are dissolved in about 30 gm. tertiarybutyl-chloride and 2 gm. aluminum chloride or zinc chloride or the likeare added. The reaction soon sets in at room temperature with theformation of hydrochloric acid. Furformaldehyde employed exceeds thequantity.

which can be taken up by the phenolic body. By acidifying, a softresinous condensation product is obtained which, if desired, may beconverted into a solid resin.

vlBoth condensation products are readily soluble in drying oils in thecold even before entering into reaction. By the application of heat thetypical hardening effects are obtained. Due to their good solubility indrying oils, the condensation products may also be used as bases for ibaking varnishes, the hardening reactionbeing eifected afterapplication. of the varnish. In this case preferably smallerproportionsof the drying oil, especially heavy bodied oils, should i beemployed. Particularly hard and resistant coats are obtained in thisway, as described in my prior specifications.

Example 7 The total quantity of phenolic body obtained when, proceedingaccording to Example 6, and 85 gm. ortho phenyl-phenol are left incontact with 160 gm. of aqueous formaldehyde. with the aid of a strongalkali for about.20 days. .-:A viscous condensation product isobtainedaftermeutralization which, if desired, may be converted into asolid resin. The condensation products which show all typical hardeningproperties are readily soluble in warm drying oils and form permanent-1y clear reaction products when heated to reaction temperatures.

Example 8 resinous mass.

It dissolves readily in warm drying oils, already at temperaturesconsiderably below reaction temperatures. Through reaction, permanentlyclear products are obtained. of particularly high value. The alkaliresistance of coatings resulting from these interaction products isstill superior to those deriving from phenols having nometasubstituents. Example 9 The tertiary-butyl group is substitutedaccording to known methods in the symmetric 1,3,5 xylenol of a meltingpoint of 64. Three parts of the substituted product and 1 part ofbenzene or its homologues, and part of concentrated aqueous alkalisolution form, after prolonged shaking, a nearly homogeneous reactionmixture. Itis kept at temperatures between 40 and 60-for 2 days. If thereaction mixture becomes considerably unhomogeneous, more of thesolvents men-v tioned should he added. The reaction mixture is slightlyacidified and the aqueous layer separated from the solvents whichcontain the con: densation product. This solution may be used directlyfor combining the condensation product with drying oils, etc., or thesolvent may be evaporated first. In this way a solid resinouscondensation product is obtained which, is readily soluble in dryingoils and is capable of bringing about an intense hardening effect.

Also, interaction products from this condensation product with dryingoils and stuffs containing the same, ester gums, etc., show aparticularly high alkali resistance, similar to the results broughtabout with the condensation products obtained according to Example 8.Also when substituting in the xylenol mentioned propylor amylor stillhigher groups, useful results are obtained."

trample suitable .way from the ortho-cresol used in excess.

suchasbyvacuumdistillation.watersteamdistiilatiomorwashing with dilutedalkalis.

About 3 parts aqueous formaldehyde and 55 part oi soda-lye (40%) formaclear reaction mixture with the intermediary product obtained above.'lhemixtureiskeptforseveraldays at 40' 0., By neutralising, acondensation product isobtainedwhichiav'iscousatOOandsolid at room'temperatiu'e.

It dissolves in sligh ly warmed drying oils and on reacting with oilssome of its intense brownred color disappears. The reaction products arepermanently clear and show excellent properties. Also, a fairlight-proofness can be noticed when intermediate products are used whichare carefully liberated from ortho-cresol, while orthocresol itselftends to exhibit very annoying yellowing phenomena.

Hardening formaldehyde condensation prod ucts having still better oilsolubility are obtained when substituting the ketone by still higherhomologues, such as methyl-butyl-ketone or ethyl-propyl-ketone. or bycyclic ketones. such as cyclo-hexanone or methyl-cyclo-hexanones. Butalso the employment of the lower molecular metbyl-ethyl-ketone finallyleads to. hardening condensation products having a fair compatibilitywith oils.

The condensation products in the preceding examples may also be causedto react with other basic materials used in the varnish and lacquerfield, particularly such as contain drying oils in physical mixture orchemical combination. In this connection I wish to mention thosemixtures obtained from natural or modified or artificial resins withdrying oils or mixed esters which are obtained from polyhydric alcoholswith both polybasic and monobasic carboxylic acids. including thosederiving from drying oils.

What I claim is: a

1. An artificial mass having a very high alkali A resistance whichcomprises the reaction product of (1) at leastone material selected fromthe class consisting of substantially neutral varnish raw materials andwaxes with (2) a heat hardening condensation product obtained bycondensing, with the aid of a strongly alkaline catalyst. a substantialexcess of formaldehyde over the equimolecular quantity with asubstantially pure phenol having only two particularly reactivepositions unoccupied and carrying a plurality of substituents whicharemembers of a group con-- sisting of hydrocarbon radicals andchlorine. one 0! said substituents being in the meta-position, saidphenol complying with the rule that the total number of saturated carbonatoms present in the molecule is at least three per each phenolic group.carbon atoms of methyl groups in metaposition to phenolic hydroxy groupsnot being calculated in this number.

2. Aprocessforforminganartificialmasshavingaveryhighaikali resistancewhich reacting together by pplication of heat (1) atleastonematerialselectedfromtheclassconaistingofsubstantiallyneutralvamishrawmateriaisand wanes and (2) aheathardening condensation product in which asubstantial excess of formaldehyde over the equimolecular quantityupto2molsiscompounded,withtheaidofa strongly alkaline catalyst, with onemol. of a substantially pure phenol having only two particularlyreactive positions unoccupied and carrying a plurality of substituentswhich are members of the group consisting of hydrocarbon radicals andchlorine, one of said substituents being in the meta-position, saidphenol complying with the rule that the total number of saturated carbonatoms present in the molecule is at least three per each phenolic group,carbon atoms of methyl groups in meta-position to phenolic hygeroxygroups not being calculated in this num- 3. A process for producingvarnish basic material of particularly high alkali resistance, whichcomprises reacting together by application of heat (1) at least onematerial selected from the class consisting of substantially neutralvarnish raw materials and waxes and (2) a heat hardening condensationproduct obtained by condensing. with the aid of a strongly alkalinecatalyst, a substantial excess of formaldehyde over the equimolecularquantity with a phenol in which only two of the particularly reactivepositions are unoccupied and which carries a plurality of substituentswhich are members of the group consisting of hydrocarbon radicals andchlorine, one of said substituents being in the meta-position, and whichphenol is substituted at least in one meta-position, the total number ofsaturated carbon atoms being at least three per each phenolic group.carbon atoms oi methyl groups in meta-position to phenolic hydroxygroups not being calculated in this number.

4. A composition of matter of particularly high alkali resistanceobtained according to claim 3.

5. An artificial mass according to claim 1, wherein the catalystemployed is a caustic alkali.

6. A process according to claim 2, wherein the catalyst employed isselected from a group consisting of caustic soda and caustic potash.

HERBERT HONEL.

